Process for producing ester or alcohol

Abstract

Provided is a process for producing an ester or alcohol using a fluoroimidinium sulfonate derivative represented by the general formula (9) or a fluoroimidinium carboxylate derivative represented by the general formula (6) and using as a raw material alcohol involving inversion of steric configuration. Further provided are a fluoroimidinium sulfonate derivative represented by the general formula (9), and a process for producing the same.

1 . A process for producing an ester or alcohol having an inverted steric configuration with respect to alcohol serving as a raw material, the process comprising reacting an optically active alcohol or a geometrically isomeric alcohol with a compound represented by the general formula (1): 
     
       
         
         
             
             
         
       
       [wherein R1 and R2 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero ring, and may be the same as or different from each other, R1 and R2 may be bonded to each other to form a ring containing a nitrogen atom, or a nitrogen atom and other heteroatom, a represents a hydrogen atom, a substituent represented by the general formula (2): 
     
     
       
         
         
             
             
         
       
       (wherein R4 and R5 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero ring, and may be the same as or different from each other, R4 and R5 may be bonded to each other to form a ring containing a nitrogen atom, or a nitrogen atom and other heteroatom, or R1 and R4 may be bonded to each other to form a ring containing a nitrogen atom), or a substituent represented by the general formula (3): 
     
     
       
         
         
             
             
         
       
       (wherein R6 represents a fluorine atom, or an alkyl group that is partially or fully substituted with fluorine atom(s)), X represents a compound represented by the general formula (4): 
     
     
       
         
         
             
             
         
       
       (wherein R3 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero ring), or by the general formula (5): 
     
     
       
         
         
             
             
         
       
       (wherein R3 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero ring)]. 
     
   
   
       2 . The process for producing an ester or alcohol as set forth in  claim 1 , wherein in the compound represented by the general formula (1), X is represented by the general formula (4), and the process comprises obtaining a sulfonic acid ester. 
   
   
       3 . The process for producing an ester or alcohol as set forth in  claim 1 , wherein the compound represented by the general formula (1) is represented by the general formula (6): 
     
       
         
         
             
             
         
       
       (wherein R1, R2, R3 and A each have the same meanings as defined in the general formula (1)), and the process comprises obtaining a carboxylic acid ester or alcohol. 
     
   
   
       4 . The process for producing an ester or alcohol as set forth in  claim 3 , wherein the compound represented by the general formula (6) is represented by the general formula (7): 
     
       
         
         
             
             
         
       
       (wherein R1, R2 and A each have the same meanings as defined in the general formula (1)), and the process comprises obtaining a carboxylic acid ester or alcohol. 
     
   
   
       5 . The process for producing an ester or alcohol as set forth in  claim 2 , wherein the optically active alcohol or the geometrically isomeric alcohol is an optically active secondary alcohol, and the process comprises obtaining a sulfonic acid ester. 
   
   
       6 . The process for producing an ester or alcohol as set forth in  claim 3 , wherein the optically active alcohol or the geometrically isomeric alcohol is an optically active secondary alcohol, and the process comprises obtaining a carboxylic acid ester or alcohol. 
   
   
       7 . The process for producing an ester or alcohol as set forth in  claim 5 , wherein the optically active secondary alcohol is represented by the general formula (8): 
     
       
         
         
             
             
         
       
       (wherein R8 represents a hydrogen atom, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid amide R9 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group, the symbol * represents that the hydroxyl group is optically active, indicating a compound in either an R- or an S-form), and the process comprises obtaining a sulfonic acid ester. 
     
   
   
       8 . The process for producing an ester or alcohol as set forth in  claim 6 , wherein the optically active secondary alcohol is represented by the general formula (8): 
     
       
         
         
             
             
         
       
       (wherein R8 represents a hydrogen atom, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid amide, R9 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group the symbol * represents that the hydroxyl group is optically active, indicating a compound in either an R- or an S-form), and the process comprises obtaining a carboxylic acid ester or alcohol. 
     
   
   
       9 . A compound represented by the general formula (9): 
     
       
         
         
             
             
         
       
       [wherein R1, R2, and R3 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero ring, and may be the same as or different from each other, R1 and R2 may be bonded to each other to form a ring containing a nitrogen atom, or a nitrogen atom and other heteroatom, a represents a hydrogen atom, a substituent represented by the general formula (2) 
     
     
       
         
         
             
             
         
       
       (wherein R4 and R5 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted hetero ring, and may be the same as or different from each other, R4 and R5 may be bonded to each other to form a ring containing a nitrogen atom, or a nitrogen atom and other heteroatom, or R1 and R4 may be bonded to each other to form a ring containing a nitrogen atom), or a substituent represented by the general formula (3): 
     
     
       
         
         
             
             
         
       
       (wherein R6 represents a fluorine atom, or an alkyl group that is partially or fully substituted with fluorine atom(s))]. 
     
   
   
       10 . The compound as set forth in  claim 9 , wherein the compound represented by the general formula (9) is represented by the general formula (10): 
     
       
         
         
             
             
         
       
       (wherein R1 to R5 each have the same meanings as defined in the general formula (9)). 
     
   
   
       11 . The compound as set forth in  claim 9 , wherein the compound represented by the general formula (9) is represented by the general formula (11): 
     
       
         
         
             
             
         
       
       (wherein R1 to R3 each have the same meanings as defined in the general formula (9)). 
     
   
   
       12 . The compound as set forth in  claim 9 , wherein the compound represented by the general formula (9) is represented by the general formula (12): 
     
       
         
         
             
             
         
       
       (wherein R1 to R3 each have the same meanings as defined in the general formula (9), or R7 represents a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, that is fully substituted with fluorine atoms). 
     
   
   
       13 . The compound as set forth in  claim 10 , wherein in the compound represented by the general formula (10), R1, R2, R4, and R5 are each independently an alkyl group having 1 to 6 carbon atoms. 
   
   
       14 . The compound as set forth in  claim 10 , wherein the compound represented by the general formula (10) is represented by the general formula (13): 
     
       
         
         
             
             
         
       
       (wherein R3 has the same meaning as defined in the general formula (9)). 
     
   
   
       15 . A process for producing a compound represented by the general formula (9): 
     
       
         
         
             
             
         
       
       [wherein R1, R2, R3, and A each have the same meanings as defined below], 
       the process comprising reacting a compound represented by the general formula (14): 
     
     
       
         
         
             
             
         
       
       [wherein R1 and R2 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero ring, and may be the same as or different from each other, R1 and R2 may be bonded to each other to form a ring containing a nitrogen atom, or a nitrogen atom and other heteroatom; A represents a hydrogen atom, a substituent represented by the general formula (2): 
     
     
       
         
         
             
             
         
       
       (wherein R4 and R5 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero ring, and may be the same as or different from each other, where R4 and R5 may be bonded to each other to form a ring containing a nitrogen atom, or a nitrogen atom and other heteroatom; or R1 and R4 may be bonded to each other to form a ring containing a nitrogen atom), or a substituent represented by the general formula (3): 
     
     
       
         
         
             
             
         
       
       (wherein R6 represents a fluorine atom, or an alkyl group that is partially or fully substituted with fluorine atom(s)); any one of the fluorine atoms on the carbon atoms bonded with the nitrogen atoms may be anions to form ion-pairs] with a compound represented by the general formula (15): 
     
     
       
         
         
             
             
         
       
       (wherein R3 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero ring; M +  represents an alkali metal ion or an alkaline earth metal ion). 
     
   
   
       16 . The process as set forth in  claim 15 , wherein the compound represented by the general formula (14) is represented by the general formula (16): 
     
       
         
         
             
             
         
       
       (wherein R1, R2, R4, and R5 each have the same meanings as defined in the general formula (14), and any one of the fluorine atoms on the carbon atoms bonded with the nitrogen atoms may be anions to form ion-pairs). 
     
   
   
       17 . The process as set forth in  claim 15 , wherein the compound represented by the general formula (14) is represented by the general formula (17): 
     
       
         
         
             
             
         
       
       (wherein R1 and R2 each have the same meanings as defined in the general formula (14), and any one of the fluorine atoms on the carbon atoms bonded with the nitrogen atoms may be anions to form ion-pairs). 
     
   
   
       18 . The process as set forth in  claim 15 , wherein the compound represented by the general formula (14) is represented by the general formula (18): 
     
       
         
         
             
             
         
       
       (wherein R1 and R2 each have the same meanings as defined in the general formula (14), R7 represents a fluorine atom, or an alkyl group having 1 to 6 carbon atoms, that is fully substituted with fluorine atoms, and any one of the fluorine atoms on the carbon atoms bonded with the nitrogen atoms may be anions to form ion-pairs, or the hydrogen fluoride may leave to make an olefinic compound). 
     
   
   
       19 . The process as set forth in  claim 15 , wherein the compound represented by the general formula (14) is the compound in which R1, R2, R4, and R5 are each an alkyl group having 1 to 6 carbon atoms. 
   
   
       20 . The process as set forth in  claim 15 , wherein the compound represented by the general formula (14) is represented by the formula (19): 
     
       
         
         
             
             
         
       
     
   
   
       21 . A process for producing a sulfonic acid ester, comprising reacting alcohol with a compound represented by the general formula (9): 
     
       
         
         
             
             
         
       
       [wherein R1, R2, and R3 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted hetero ring, and may be the same as or different from each other, R1 and R2 may be bonded to each other to form a ring containing a nitrogen atom, or a nitrogen atom and other heteroatom, a represents a hydrogen atom, a substituent represented by the general formula (2): 
     
     
       
         
         
             
             
         
       
       (wherein R4 and R5 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero ring, and may be the same as or different from each other, R4 and R5 may be bonded to each other to form a ring containing a nitrogen atom, or a nitrogen atom and other heteroatom, or R1 and R4 may be bonded to each other to form a ring containing a nitrogen atom), or a substituent represented by the general formula (3) 
     
     
       
         
         
             
             
         
       
       (wherein R6 represents a fluorine atom, or an alkyl group that is partially or fully substituted with fluorine atom(s)). 
     
   
   
       22 . The process for producing an ester or alcohol as set forth in  claim 4 , wherein the optically active alcohol or the geometrically isomeric alcohol is an optically active secondary alcohol, and the process comprises obtaining a carboxylic acid ester or alcohol. 
   
   
       23 . The process for producing an ester or alcohol as set forth in  claim 22 , wherein the optically active secondary alcohol is represented by the general formula (8): 
     
       
         
         
             
             
         
       
       (wherein R8 represents a hydrogen atom, a carboxylic acid, a carboxylic acid ester, or a carboxylic acid amide, R9 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group, the symbol * represents that the hydroxyl group is optically active, indicating a compound in either an R- or an S-form), and the process comprises obtaining a carboxylic acid ester or alcohol.